Ozonolysis operations for generation of reduced and/or oxidized product streams

ABSTRACT

The present invention relates to methods for safe and efficient use of hydrogen and oxygen in ozonolysis operations. The invention also relates to an ozonolysis process involving elements of both reductive and oxidative ozonolysis which are integrated in a continuous process. In one embodiment, the ozonolysis process of the present invention uses hydrogen and/or oxygen generated from water and electricity, which may be recycled to generate water and/or electricity.

RELATED APPLICATIONS

This application is a national stage application, filed under 35 U.S.C.§371, of International Application No. PCT/US2013/051357, filed Jul. 19,2013, which claims the benefit of and priority to U.S. ProvisionalPatent Application Nos. 61/673,411, filed Jul. 19, 2012 and 61/784,376,filed Mar. 14, 2013. The contents of each of these applications arehereby incorporated by reference in their entireties.

FIELD OF INVENTION

Embodiments disclosed herein are directed to an ozonolysis processinvolving an integrated process including both reductive and oxidativeozonolysis processes in a continuous process.

BACKGROUND

Ozonolysis is a highly atom-efficient oxidative transformation, with twoof the three oxygen atoms from the ozone molecule being incorporatedinto the products. Due to its ease of generation and its efficiency withregard to the oxidative cleavage of olefins, ozone has found use in awide variety of applications, including chemical manufacturing and waterdisinfection.

When used in chemical manufacturing, ozonolysis requires a second stepthat destroys the peroxide and/or ozonide present in the reactionmixture before products are isolated. In the case of oxidativeozonolysis, the peroxides are further heated and oxidized in thepresence of oxygen (O₂) to generate products including carboxylic acidproducts. In the case of reductive ozonolysis, the peroxides andozonides are quenched under reducing conditions, using hydrogen (H₂) togive carbonyls and/or alcohols as the major products.

All ozonolysis processes require electricity and oxygen in order togenerate ozone, and in the case of reductive ozonolysis, hydrogen may beused, as well. Historically, industrial oxygen production has beencarried out mainly through the distillation or zeolite treatment of air,while H₂ has been generated from the reformation of natural gas. SeeCooke, S. J., Industrial Gases, Kent and Riegel's Handbook of IndustrialChemistry and Biotechnology, 11^(th) ed., ch. 27, p. 1215 (2007);Hiller, H., Gas Production: Introduction, Ullmann's Encyclopedia ofIndustrial Chemistry, vol. 16, p. 403 (2012). More recently, however,electrolysis of water (H₂O) using proton exchange membranes (PEM) hasbecome a common method of oxygen and hydrogen generation as well. In theelectrolysis of water, 2 moles of hydrogen are produced for every moleof oxygen making it highly amenable to generation of starting materialsfor reductive ozonolysis processes, as both gases are required for suchprocesses.

Regardless of source, oxygen must be treated with electricity togenerate ozone for the ozonolysis process. The ozone is then carried tothe ozone reactor as a 0.1-20% mixture in a stream of oxygen. During theozonolysis reaction, only the ozone is consumed and thus the oxygen mustthen be discarded, recycled, or used for an alternative purpose. Due tothe cost associated with oxygen production, the preferred option hasbeen to recycle the oxygen for continued ozone generation, using acorona discharge technique. See Vezzù, G., et al. IEEE Transactions onPlasma Science, Vol. 37, No. 6, p. 890-896 (2009).

While this process can be relatively efficient, there is a hazardassociated with explosion due to organic contamination of the oxygenstream that is being recycled. Multiple condensers, precipitators,and/or filters are thus employed to manage this risk.

In addition to hazard reduction, the cost of electricity in thegeneration of ozone is a significant expense, and therefore a clean andefficient source of electricity would be desirable for the ozonegeneration process. Both fuel cells and hydrogen burning gas turbinesoffer such a solution. Fuel cells and gas turbines can use hydrogen andoxygen to generate electricity, with the reaction products being waterand heat. While oxygen from ambient air can be used for these fuelcells, the fuel cells run at optimum efficiency in the presence of highpurity oxygen and hydrogen. See Buchi, F. N., et al. On the Efficiencyof Automotive H ₂ /O ₂ PE Fuel Cell Systems, 3^(rd) European PEFC,Session B09 (Thursday, 7 Jul. 2005). The deficiencies in currentozonolysis processes are addressed by the current invention. Theinvention disclosed herein arranges the ozonolysis process in such a waythat the excess oxygen and hydrogen that are generated from theelectrolysis step can be used to efficiently run a fuel cell or a gasturbine, thus significantly offsetting the net electricity required togenerate ozone in a single-pass system.

SUMMARY OF THE INVENTION

The present invention relates to performing ozonolysis for generatinghydrogenated and/or oxidized ozonated products. In particular, theinvention relates to an ozonolysis process for producing linear alkylaldehydes (e.g., nonanal) and diacids (e.g., azelaic acid) oracid-esters (e.g., monomethyl azelate) by integrating both reductive andoxidative ozonolysis processes in a continuous process. The presentinvention also relates to methods of safe and/or efficient handling ofgases, for example, hydrogen and oxygen. In one embodiment, electrolysisis used to generate gases for the ozonolysis process, thereby minimizingthe need to recycle the oxygen through corona discharge. In one suchembodiment, hydrogen and/or oxygen can or may be reclaimed via fuel cellor a turbine at the end of the ozonolysis process. In anotherembodiment, hydrogen and/or oxygen can or may be used in any otheroperations for which the gases are useful.

In one embodiment, the current invention provides an ozonolysis process,which uses oxygen and hydrogen from any source, where oxygen can beutilized as a reagent for generating ozone, and ozone can then be usedin ozonolysis of fatty acid(s) and/or fatty acid ester(s) in an ozonereactor. In one embodiment, oxygen and/or hydrogen is generated byelectrical means or by any other means of hydrolysis. In additionalembodiments, oxygen and/or hydrogen is generated by any other means,including from distillation of air or from natural gas reformation.

In a process described herein, the fatty acid and/or fatty acid ester(s)can or may be inputted into the ozone reactor, where the fatty acid(s)and/or fatty acid ester(s) absorbs ozone to form an ozonated productstream. According to some elements of the current invention, theozonated product stream include, without being limited to the listedexamples, ozonides, peroxides, aldehydes, acids, esters, and anycombination thereof. The ozonated product stream, according to thecurrent invention can be used to generate hydrogenated products, forexample, linear alkyl aldehydes (e.g., nonanal) and/or oxidized oroxygenated products, for example, diacids or acid-esters.

In one embodiment, without being limiting, the current inventionprovides an ozonolysis process which uses an ozone reactor. For example,the ozone reactor is a batch reactor, a continuous stirred-tank reactor,a loop reactor, a plug flow-type reactor, or a fixed bed-type reactor.In one embodiment, a batch reactor, a continuous stirred-tank reactor,or a loop reactor is used in the ozonolysis step. In one embodiment, aplug flow-type reactor or fixed bed-type reactor is used in thehydrogenation step.

According to the embodiments of the current invention, the ozonatedproduct stream can or may be partially reduced in a hydrogenationchamber where hydrogenated products, for example, linear alkyl aldehydesare generated. In one embodiment, the mixture comprising aldehydes formsa biphasic layer as it leaves the hydrogenation chamber, one phase ofwhich is an organic phase. The organic phase can then be fractionated bydistillation or ion exchange into two or more fractions, one of whichmay comprise linear alkyl aldehydes (e.g., nonanal).

The organic phase fraction(s) not comprising linear alkyl aldehydes canor may then be oxidized in an oxidation chamber to generate oxidizedproducts, for example, diacids or acid-esters. In one embodiment, this(e.g., “remaining”) organic phase fraction comprises an oxo-acid or anoxo-ester, which is first distilled and then oxidized in an oxidationchamber. In one embodiment, the oxidation of distilled oxo-acid producesdiacid.

In another embodiment, the organic phase fraction comprising an oxo-acidor oxo-ester is first oxidized in an oxidation chamber and thendistilled, precipitated, and/or extracted to produce a diacid or esterssuch as an acid-ester and diester. In one embodiment, the diacidproduced has a purity of at least 40%, 50%, 60%, 70%, 80%, 90%, 95%, or99%.

The current invention provides that hydrogen gas can or may be streamedthrough a hydrogenation chamber for partial reduction of the ozonatedproduct stream generated from reaction of fatty acid in an ozonereactor. In an embodiment, hydrogen is streamed continuously through thehydrogenation chamber.

In an embodiment, oxygen is streamed through the oxidation chamber tooxidize the remaining organic phase fraction (with or without furtherdistillation) to produce diacids or acid-esters. Any unused or excessoxygen from ozone reactor, or oxidation chamber, or from both may berecycled as fuel for generation of ozone, water, or electricity, or anycombination thereof.

In some embodiments of the current invention, any unused hydrogen fromthe hydrogenation chamber may be recycled, for example as fuel forgeneration of water or electricity, or both.

In an embodiment, the ozonolysis process may include a catalyst tofacilitate oxidation of the ozonated product stream. In one embodiment,the catalyst may be a metal catalyst.

The invention provides that electricity may be generated in a devicesuch as a fuel cell or a hydrogen burning gas turbine. The fuel cell,according to an embodiment, may be an alkaline fuel cell, a phosphoricacid fuel cell, or a proton exchange membrane (PEM) fuel cell.

In some embodiments, the current invention provides an electrolyzer forgenerating ozone, where the electrolyzer may be a PEM hydrolysiselectrolyzer.

In another embodiment, the ozonolysis process of the current inventionmay include both oxidative and reductive processes. In some embodiments,oxygen and hydrogen used in ozonolysis process may be generated fromwater and electricity.

The current invention also provides an oxidative ozonolysis process,which may utilize oxygen as a reagent for generating ozone. The ozonegenerated may then be used to generate an ozonated product stream fromfatty acid in an ozone reactor. The fatty acid may be inputted to theozone reactor, where fatty acid may absorb ozone from the oxygen and/orozone stream, and may form an ozonated product stream, which may includeozonides, peroxides, aldehydes, and acids and/or esters. The ozonatedproduct stream may then be passed into an oxidation reactor, in whichoxygen may be streamed continuously for oxidizing the ozonated productstream.

In an embodiment of the current invention, the streaming oxygen in theoxidation chamber may create an oxidative environment for a concurrentthermal scission of ozonides and for oxidation of the ozonated product(e.g., aldehydes).

The invention also provides that any remaining oxygen during generationof ozone and/or the oxidation of ozonated product stream may then beused to generate water and/or electricity. In certain embodiments, theinvention provides that when oxygen is recycled to generate water and/orelectricity, no oxygen may be recycled into the ozone reactor andsubstantially all or all of oxygen may be utilized in the ozonolysisprocess.

In another embodiment, any oxygen unused in the generation of ozone oroxidizing ozonated product stream or both in an oxidative ozonolysisprocess may be recycled to the ozone reactor after passing throughdistillation towers.

In the oxidative ozonolysis process of some embodiments of thisinvention, oxidation of the ozonated product stream includes a catalystto facilitate oxidation. According to one embodiment of the currentinvention, a catalyst may be a metal catalyst.

In some embodiments, electricity for use in the oxidative ozonolysis maybe generated using a device, for example, a fuel cell or a hydrogenburning gas turbine.

In an embodiment of the current invention, during oxidative ozonolysis,fatty acids may be introduced to the ozone reactor in a solvent selectedfrom nonanoic acid, glycerol, water, and any combinations thereof.

An embodiment of the current invention provides that oxygen, hydrogen,and ozone may be generated in a single step. The oxygen used ingeneration of ozone may be recycled through an organic medium, whereinthe organic medium is substantially purged of volatile components. Inadditional embodiments, the oxygen used for generating ozone or foroxidizing the ozonated product stream may be recycled after being passedthrough a chamber free of volatile, light organic materials or a chambercomposed of only non-volatile, heavy organic materials.

In an embodiment, the current invention provides a reductive ozonolysisprocess integrated with the oxidative ozonolysis process, in whichoxygen can or may be used as a reagent for generating ozone and theozone can or may be used for generating an ozonated product stream fromthe fatty acid in an ozone reactor. In this embodiment, the fatty acidcan or may be inputted in the ozone reactor, where the fatty acid can ormay absorb ozone from the oxygen and/or ozone stream, and form anozonated product stream. The ozonated product stream can or may then betransferred continuously to a hydrogenation chamber for hydrogenation,where a stream of hydrogen can or may reduce the ozonated product streamto produce aldehyde-rich products. The reduced ozonated product streammay then be distilled to produce aldehyde-rich products, such as linearalkyl aldehydes (e.g., nonanal), and for generation of diacids and/oracid esters.

In an embodiment of the reductive ozonolysis process, any hydrogenremaining unused in the reduction step is then used to generate water,electricity, or in any other operation that uses or requires hydrogen,such as down-stream processing, or other hydrogenation operations. Theelectricity, according to an embodiment of the reductive ozonolysisprocess of the current invention, can be generated in a source such as afuel cell or hydrogen burning gas turbine.

The current invention also provides an ozonolysis process comprisingreductive ozonolysis and oxidative ozonolysis. In one embodiment, thereductive ozonolysis occurs prior to the oxidative ozonolysis. In oneembodiment, the process of the invention further comprises generatingozone prior to the reductive ozonolysis and the oxidative ozonolysis. Inone embodiment, the ozone generated reacts with a fatty acid to producean ozonated product.

In one embodiment, the process of the invention further comprisesreacting a fatty acid with ozone prior to the reductive ozonolysis andthe oxidative ozonolysis to produce an ozonated product. In oneembodiment, the reaction between the fatty acid and the ozone comprisesa solvent (e.g., nonanoic acid, glycerol, and water, or a combinationthereof).

In one embodiment, the ozonated product comprises an ozonide, peroxide,aldehyde, or acid.

In one embodiment, the ozonated product is reduced in a reductiveozonolysis process. In one embodiment the reduced product comprises analdehyde. In one embodiment, the reductive ozonolysis comprises acatalyst (e.g., a metal catalyst). In one embodiment, the reductiveozonolysis comprises hydrogen gas. In a further embodiment, any unusedhydrogen gas is recycled.

In one embodiment, the reduced product forms biphasic liquid layers. Inone embodiment, the process of the invention further comprisesseparating the organic phase of the biphasic liquid layers. In anotherembodiment, the process of the invention further comprises purifying(e.g., distilling, and ion-exchanging) the organic phase to obtain analdehyde. In one embodiment, the aldehyde is a linear aldehyde.

In one embodiment, the ozonated product is oxidized in an oxidativeozonolysis process. In one embodiment, the oxidized product comprises adiacid. In one embodiment, the oxidative ozonolysis process comprises acatalyst (e.g., a metal catalyst). In one embodiment, the oxidativeozonolysis process comprises oxygen. In a further embodiment, any unusedoxygen is recycled.

The current invention also provides an ozonolysis process comprising: 1)reacting a fatty acid with ozone to produce an ozonated product; 2)reducing the ozonated product under reductive ozonolysis to produce areduced product; 3) separating an aldehyde from the reduced product; 4)oxidizing the reduced product to produce an oxidized product; and 5)separating a diacid or acid ester from the oxidized product. In oneembodiment, the process of the invention further comprises generatingozone prior to step 1). In one embodiment, step 2) comprises hydrogengas. In a further embodiment, any unused hydrogen gas is recycled. Inanother embodiment, step 4) comprises oxygen. In a further embodiment,any unused oxygen is recycled.

The invention also provides partially reduced products and/or oxygenatedproducts prepared by the hybrid ozonolysis process described herein. Inone embodiment, the products produced by the methods of the inventionare linear aldehyde, oxo-acid, oxo-ester, acid-ester, and/or diacid.

Unless otherwise defined, all technical and scientific terms used hereinhave the meaning as commonly understood by one of ordinary skill in theart to which this invention pertains. In the specification, the singleforms also include the plural unless the context clearly dictatesotherwise. Although methods and materials similar or equivalent to thosedescribed herein can be used in the practice or testing of the presentinvention, suitable methods and materials are described below. Inaddition, the materials, methods, and examples are illustrative only andare not intended to be limiting.

Other features and advantages of the invention will be apparent from thedetailed description and claims.

In order to understand the invention and to demonstrate how it may becarried out in practice, embodiments are now described, by way ofnon-limiting examples, with reference to the accompanying drawings.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows a representative schematic of hybrid ozonolysis of oleicacid to generate diacids and linear alkyl aldehydes. Oleic acid is usedonly as an example.

FIG. 2 shows representative schematic of gas flow through a hybrid ofthe reductive and oxidative ozonolysis processes, where the unbrokenlines marked with I-IV and the unbroken lines with arrows directing awayfrom chambers C and D represent the flow of organic reactants andproducts.

FIG. 3 shows a Flame Ionization Detector Gas Chromatography (GC FID)trace of the algal fatty acid methyl esters used for certain hybridozonolysis experiments. The included table shows the free fatty acidcomposition.

FIG. 4 shows a GC FID trace of the organic phase after reductiondescribed in Example 3. Note that the nonanal peak is at ˜6.4 minutes,the internal standard at ˜12.8 minutes, and nonanoic acid at ˜14.1minutes.

FIG. 5 shows a GC FID trace of the distillate collected from hybridozonolysis of algal fatty acid described in Example 3. Integrationsuggests >97% nonanal, represented by the peak at ˜6.4 minutes.

FIG. 6 shows a GC FID trace of the heavy residue recovered afterdistillation and methyl ester and dimethyl acetal derivatizationdescribed in Example 3. From left to right, nonanal dimethyl acetal(5.364 min), nonanoic methyl ester (5.608 min), azelaldehyde (i.e.,9-oxononanoic acid) methyl ester (9.996 min), azelaldehyde methyl esterdimethyl acetal (10.214 min), azelaic acid dimethyl ester (10.508 min),palmitic acid methyl ester (10.982 min), and stearic acid (13.087 min).

FIG. 7 shows a GC FID trace of azelaic acid obtained from the hybridozonolysis process after methyl ester derivatization. Integrationsuggests >97% azelaic acid.

FIG. 8 shows a ¹H NMR of the nonanal described in FIG. 5, with CDCl₃used as solvent.

FIG. 9 shows ¹H NMR of the azelaic acid described in FIG. 7, with CDCl₃used as solvent.

FIG. 10 shows GC FID trace of monomethyl brassylate after the hybridozonolysis process after methyl ester derivatization. Integrationsuggests 96.5% monomethyl brassylate.

FIG. 11 shows ¹H NMR of the monomethyl brassylate described in FIG. 10,with CDCl₃ used as solvent.

DETAILED DESCRIPTION OF THE INVENTION

The materials, articles, and methods described herein may be understoodmore readily by reference to the following detailed description ofspecific aspects of the disclosed subject matter and the Examplesincluded therein. Before the present materials, articles, devices, andmethods are disclosed and described, it is to be understood that theaspects described below are not limited to specific methods or specificreagents, and as such may vary. It is also to be understood that theterminology used herein is for the purpose of describing particularaspects only and is not intended to be limiting.

Also, throughout this specification, various publications includingpatent documents and scientific articles are referenced. The disclosuresof these publications in their entireties are hereby incorporated byreference into this application in order to more fully describe thestate of the art to which the disclosed matter pertains. The referencesdisclosed are also individually and specifically incorporated byreference herein for the material contained in them that is discussed inthe sentence in which the reference is relied upon.

The following paragraphs describe the invention, but only as an exampleand in no way limited solely to what is expressly disclosed. Anyinherent or well established method in the art, which may be in use atthe time of invention of the current embodiments and/or any improvementsthereof, are inherently incorporated herein.

Hybrid Ozonolysis

Unlike the processes disclosed in the art, this invention describes anozonolysis process specifically for producing linear alkyl aldehydes(e.g., nonanal) and diacids (e.g., azelaic acid) or acid-esters (e.g.,monomethyl azelate) by integrating both reductive and oxidativeozonolysis processes in a continuous process. The ozonolysis process ofthe current invention is referred to as a hybrid ozonolysis process.

The hybrid ozonolysis process described herein may be used to generateboth diacids (and/or acid-esters) and linear alkyl aldehydes from theozonolysis of unsaturated fatty acids and/or fatty acid esters.

In contrast, previous ozonolysis processes have been limited to productsets that result in either acid and/or ester products (i.e., oxidativeozonolysis), or aldehyde and/or alcohol products (i.e., reductiveozonolysis). For example, oxidative ozonolysis processes were describedin U.S. Pat. No. 2,813,113 and US Patent Application 2012/0245375, andthe reductive ozonolysis of fatty acids in aqueous conditions wasdescribed in U.S. Pat. No. 3,504,038. Other related processes have beendescribed in 1) US 2005/0010069 A1, which uses alcoholic processingconditions to form resins; 2) WO 2010/078498 A1, which uses alcoholssuch as glycerol in the process to generate polyols for resins; 3) WO2012/168770 A1, which uses ozone to make formulations of medicinalinterest; 4) WO 2010/011134 and U.S. Pat. No. 7,825,277 which describegeneral ozonolysis using microreactors; and 5) U.S. Pat. No. 5,543,565,which describes a method for enhancing azelaldehyde oxidation using afritted tube.

In one embodiment of the invention, the purity of the linear aldehyde,oxo-acid, oxo-ester, acid-ester, and/or diacid produced by the methodsdescribed herein is more than about 45%. In one embodiment, the purityof the linear aldehyde, oxo-acid oxo-ester, acid-ester, and/or diacidproduced by the methods of the present invention is more than about 60%.In one embodiment, the purity of the linear aldehyde, oxo-acid,oxo-ester, acid-ester, and/or diacid produced by the methods of thepresent invention is more than about 70%. In one embodiment, the purityof the linear aldehyde, oxo-acid, oxo-ester, acid-ester, and/or diacidproduced by the methods of the present invention is more than about 80%.In one embodiment, the purity of the linear aldehyde, oxo-acid,oxo-ester, acid-ester, and/or diacid produced by the methods of thepresent invention is more than about 90%. In one embodiment, the purityof the linear aldehyde, oxo-acid, oxo-ester, acid-ester, and/or diacidproduced by the methods of the present invention is more than about 95%.In one embodiment, the purity of the linear aldehyde, oxo-acid,oxo-ester, acid-ester, and/or diacid produced by the methods of thepresent invention is more than about 99%.

The hybrid ozonolysis process of the current invention involves bothreduction and oxidation steps of fatty acid(s) and/or fatty acidester(s), which are carried out in the same integrative process toobtain aldehydes and/or alcohols, as well as acids and esters. SeeFIG. 1. In this method a fatty acid and/or fatty acid ester may beinputted in a solvent selected from nonanoic acid, glycerol, water, andany combination thereof, where the fatty acid and/or fatty acid esterabsorbs ozone from the oxygen and/or ozone stream in an ozone reactor,thereby forming a mixture of ozonated products or product stream, forexample, ozonides, peroxides, acids, esters and/or aldehydes. Hydrogencan then be streamed through a hydrogenation chamber for partialreduction of the ozonated product stream formed in the ozone reactor toproduce an aldehyde mixture. One fraction of the aldehyde mixtureproduced in the hydrogenation chamber may be distilled off, and a secondfraction (e.g., “remaining fraction”) of the aldehyde mixture may thenbe oxidized in an oxidation chamber with oxygen to produce acids. The“hybrid ozonolysis” approach may be used to generate optimal productsthrough ozonolysis of fatty acid(s) and/or fatty acid ester(s), forexample, linear alkyl aldehydes and diacids and esters (i.e., acid-esteror diester).

The hybrid ozonolysis process may be especially beneficial whenconverting oils and fatty acid mixtures that have high monounsaturatedfatty acid content. These mixtures may include high oleic safflower,sunflower, and canola oils, as well as tailored algae oils withcontrolled chain lengths, saturation levels and functional groupadditions. The monounsaturation may occur at a variety of positions inthe fatty acid chain to give preferred mixtures of diacid and linearaldehyde. The diacids and acid-esters may for example be used inpolymers, lubricants, cosmetics, pharmaceuticals, and agrochemicals andthe like. The linear alkyl aldehydes may for example be used directly inflavors and fragrances, or as precursors to flavors and fragrances,Guerbet alcohols, plasticizers, surfactants, and various other specialtychemicals, and the like.

The current invention provides an ozonolysis process, which may useoxygen and hydrogen, where oxygen may be utilized as a reagent forgenerating ozone, and ozone may then be used in ozonolysis of fatty acidin an ozone reactor. The ozonolysis process of the current invention mayuse oxygen and hydrogen generated from water either by electrical meansor by any other means of hydrolysis, or oxygen and hydrogen generated byany other means, as well, including from the distillation of air or fromnatural gas reformation. The fatty acid may be inputted into the ozonereactor, where it absorbs the ozone, to form an ozonated product stream.According to some elements of the current invention, the ozonatedproduct stream may include, without being limiting, peroxides,aldehydes, acids, esters, and any combination thereof. The ozonatedproduct stream, according to the current invention is used to generatelinear alkyl aldehydes (e.g., nonanal) and diacids.

According to the embodiments of the current invention the ozonatedproduct stream may be partially reduced in a hydrogenation chamber wherealdehydes are generated. The mixture comprising aldehydes may form abiphasic layer while leaving the hydrogenation chamber one phase ofwhich is an organic phase. The organic phase may then be fractionated totwo or more fractions. One of the fractions, according to someembodiments of the current invention, may contain linear alkyl aldehyde,for example (without limiting to the examples herein) hexanal, heptanal,octanal, nonanal, decanal, undecanal, dodecanal, or tridecanal. Anotherorganic phase fraction may contain an oxo-acid and or/ester, for example(without limiting to the examples herein) 12-oxododecanoic acid,11-oxoundecanoic acid, 10-oxodecanoic acid, 9-oxononanoic acid,8-oxooctanoic acid, 7-oxoheptanoicacid, or 6-oxohexanoic acid or theircorresponding esters. In one embodiment of hybrid ozonolysis describedherein, the fraction containing the oxo-acid is carried onto oxidationto form a diacid.

Accordingly, the present invention also relates to the partially reducedproducts produced by the hybrid ozonolysis process described herein. Inone embodiment, the invention relates to oxo-acid or oxo-ester producedby a method that includes (a) providing oxygen and hydrogen, whereinsaid oxygen is utilized as a reagent for generating ozone; wherein saidozone is used in ozonolysis of a fatty acid or fatty acid ester in anozone reactor; (b) inputting said fatty acid or fatty acid ester intosaid ozone reactor, in which said fatty acid or fatty acid ester absorbssaid ozone, thereby forming a mixture comprising ozonated product streamcomprising one or more compounds selected from ozonides, peroxides,aldehydes, esters, and acids; and (c) generating a plurality ofpartially reduced products comprising linear alkyl aldehydes and saidoxo-acid or oxo-ester by: (i) partially reducing said ozonated productstream after said ozonated product stream enters a hydrogenation chamberto generate said plurality of partially reduced products comprisinglargely aldehydes, wherein said aldehydes, when in the presence ofwater, form two layers comprising an organic phase while leaving thehydrogenation chamber; (ii) fractionating said organic phase to separatelinear alkyl aldehydes from the remaining organic phase which comprisessaid oxo-acid or oxo-ester; and (iii) separating said oxo-acid oroxo-ester from the remaining organic phase after fractionation at step(ii); thereby generating said oxo-acid or oxo-ester in pure form. Insome embodiments, the separation at step (iii) is performed bydistillation. In some embodiment, at least a portion of the separatedoxo-acid or oxo-ester is delivered to an oxidation chamber, resulting inthe generation of oxygenated products comprising a diacid or acid-ester.In other embodiments, the separated oxo-acid or oxo-ester is not subjectto oxidation to generate a diacid or acid-ester.

In an embodiment, the mixture leaving the hydrogenation chamber isbiphasic in the presence of water, where a coalescer and/or phaseseparator can or may be used to separate the organic phase from theaqueous phase. The coalescer, according to the current invention can be,without being limited to the examples herein, PALL'S PHASESEP® A/SSeries Liquid/Liquid Coalescer, PALL'S PHASESEP® Coalescer, or PALL'SPHASESEP® FR1 Series Liquid/Liquid Coalescer. The phase separator,according to the current invention can be, without being limited to theexample herein, a centrifuge such as Rousselet Robatel Centrifugalliquid/liquid separators.

In one embodiment, the organic phase fraction comprises an oxo-acid oroxo-ester, which is first distilled and then oxidized in an oxidationchamber. The oxidation of distilled oxo-acid or oxo-ester producesdiacid or acid-ester.

In another embodiment, the organic phase fraction comprising oxo-acid oroxo-ester leaving the hydrogenation chamber is first oxidized in anoxidation chamber and then further distilled, precipitated, and/orextracted to produce pure diacid or acid-ester.

According to the current invention, diacid or acid-ester may be producedin one of two ways. In one embodiment oxo-acid or oxo-ester may bedistilled out from the product mixture and then “pure” oxo-acid oroxo-ester may be oxidized to get pure diacid or acid-ester. In anotherembodiment, oxo-acid or oxo-ester may be oxidized in the “impure”product stream, and then the diacid or acid-ester may be separatedafterwards by distillation, precipitation and/or extraction.

A catalyst may be used to facilitate oxidation in the oxidation reactorand/or hydrogenation in the hydrogenation reactor, when the mixture ofozonides, peroxides, acids, esters and/or aldehydes may be transferredcontinuously through the reactor(s). In one embodiment, the catalyst isa metal catalyst. The catalyst can be any metal, for example, withoutbeing limiting, Mn (Manganese). Other catalysts suitable for the methodsof the current invention are: Pt (Platinum), Pd (Palladium), Ni(Nickel), Ru (Ruthenium), and other commercially available catalystssuitable for use in ozonolysis.

In an embodiment of the current invention, the oxo-acid or oxo-ester inone of the fractions during ozonolysis is then be oxidized to itscorresponding diacid or acid-ester in the presence of oxygen gas and anoptional catalyst that includes, without being limited to the examplesherein, Mn (Manganese), Os (Osmium), Pt (Platinum), Pd (Palladium), Cu(Copper), or Ru (Ruthenium), any commercially available catalystsuitable for use in oxidation, or any combination thereof.

Ozonolysis of olefins can or may be performed at moderate to elevatedtemperatures whereby the initially formed molozonide rearranges to theozonide, which can or may then be converted to a variety of products.Although not wishing to be bound by theory, it is presently believedthat the mechanism of this rearrangement involves dissociation into analdehyde and an unstable carbonyl oxide, which recombine to form theozonide.

In one embodiment, hybrid ozonolysis of a fatty acid is performed togenerate an acid and/or an aldehyde. In one embodiment, fatty acid ispassed through an ozone reactor as a thoroughly mixed emulsion in water.In one embodiment, if the mixture leaving the hydrogenation chamber isbiphasic in the presence of water, a coalescer and/or phase separator isused to separate the desired organic phase from the aqueous layer. Inone embodiment, the organic phase is fractionated by distillation or ionexchange to give a fraction containing an aldehyde. In one embodiment,the remaining organic phase after fractionation is oxidized afterentering into an oxidation chamber, resulting in the generation ofoxygenated products comprising diacids and/or acid-esters. In oneembodiment, the balance of the organic mixture is further distilled togenerate a high purity fraction of an oxo-acid or oxo-ester. In oneembodiment, the oxo-acid is oxidized in an oxidation chamber. Forexample, oxo-acid or oxo-ester is taken on wholly to be oxidized in anoxidation chamber with diacid or acid-ester being recovered in highpurity after oxidation by distillation, precipitation, and/orextraction. In one embodiment, excess oxygen and/or hydrogen may berecovered for alternate use, recycled, or discarded.

In one embodiment, hybrid ozonolysis is performed on a fatty acid andthe ozonated product stream is then partially hydrogenated to produce analdehyde in a hydrogenation reactor. In one embodiment, the aldehyde isdistilled off in a distiller or a distillation tower. In one embodiment,the remaining ozonated product stream is oxidized in an oxidationchamber to generate acids. In one embodiment, excess oxygen and excesshydrogen are fed into a fuel cell to generate electricity and/or water.For example, excess oxygen may be recycled to the ozone reactor.

The current invention also provides an ozonolysis process comprisingreductive ozonolysis and oxidative ozonolysis. In one embodiment, thereductive ozonolysis occurs prior to the oxidative ozonolysis. In oneembodiment, the process of the invention further comprises generatingozone prior to the reductive ozonolysis and the oxidative ozonolysis. Inone embodiment, the ozone generated reacts with a fatty acid to producean ozonated product.

Ozone used in the process of the invention may be generated by anymethod known in the art. For example, ozone may be generated by thevarious methods described herein.

In one embodiment, the process of the invention further comprisesreacting a fatty acid with ozone prior to the reductive ozonolysis andthe oxidative ozonolysis to produce an ozonated product. In oneembodiment, the reaction between the fatty acid and the ozone comprisesa solvent (e.g., nonanoic acid, glycerol, and water, and a combinationthereof).

A fatty acid is a carboxylic acid with long aliphatic hydrocarbonchains. The aliphatic hydrocarbon chains may be either saturated orunsaturated and may contain from at least 3 carbon atoms. For example,the aliphatic hydrocarbon chains may contain 3, 4, 5, 6, 7, 8, 9, 10,11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28,29, 30, or more carbon atoms.

The solvent for the reaction between the fatty acid and the ozone can beany solvent suitable for carrying out the reaction. For example, thesolvent may be aqueous or non-aqueous. For example, the solvent may bean acid or an alcohol. For example, the acid may be a carboxylic acid(e.g., RC(O)OH). For example, the carboxylic acid is nonanoic acid. Forexample, the alcohol is a polyol (i.e., a compound having more than onehydroxyl groups). For example, the polyol is glycerol. For example, thesolvent may be water.

In one embodiment, the ozonated product comprises an ozonide, peroxide,aldehyde, or acids (e.g., carboxylic acids). In a further embodiment,the ozonated product may comprise additional products, such as esters.

In one embodiment, the ozonated product is reduced in a reductiveozonolysis process. In one embodiment the reduced product comprises analdehyde. In one embodiment, the reductive ozonolysis process comprisesa catalyst (e.g., a metal catalyst). In one embodiment, the reductiveozonolysis process comprises hydrogen gas. In a further embodiment, anyunused hydrogen gas is recycled.

The catalyst can be any catalyst suitable for conducting reductiveozonolysis known in the art. For example, the catalyst is selected fromthe catalyst described herein.

The hydrogen gas that is not consumed in the reductive ozonolysisprocess may be recycled and/or reused. For example, the unused hydrogengas may be used for generation of water or electricity, or both, asdescribed herein.

In one embodiment, the reduced product forms biphasic liquid layers. Inone embodiment, the process of the invention further comprisesseparating the organic phase of the biphasic liquid layers. In anotherembodiment, the process of the invention further comprises purifying(e.g., distilling, and ion-exchanging) the organic phase to obtain analdehyde. In one embodiment, the aldehyde is a linear aldehyde.

The product after the reductive ozonolysis comprises aldehyde (e.g.,alkyl aldehyde). For example, the alkyl aldehyde is a linear alkylaldehyde (e.g., nonanal). For example, the aldehyde is at least 40%,50%, 60%, 70%, 80%, 90%, 95%, or 95% pure. The product after thereductive ozonolysis may also comprise oxo-acid or oxo-ester. Forexample, the oxo-acid or oxo-ester is 9-oxononanoic acid or 9-oxononanoate methyl ester). For example, the oxo-acid or oxo-ester is atleast 40%, 50%, 60%, 70%, 80%, 90%, 95%, or 95% pure.

In one embodiment, the ozonated product is oxidized in an oxidativeozonolysis process. In one embodiment, the oxidized product comprises adiacid or acid-ester. In one embodiment, the oxidative ozonolysiscomprises a catalyst (e.g., a metal catalyst). In one embodiment, theoxidative ozonolysis comprises oxygen. In a further embodiment, anyunused oxygen is recycled.

In one embodiment, the ozonated product undergoes oxidative ozonolysisafter the reductive ozonolysis of the ozonated product is performed. Forexample, the organic phase of the biphasic liquid layers formed by thereduced product undergoes oxidative ozonolysis.

The catalyst can be any catalyst suitable for conducting oxidativeozonolysis known in the art. For example, the catalyst is selected fromthe catalyst described herein.

The product after the oxidative ozonolysis comprises diacid and/oracid-ester. For example, the diacid or acid-ester is azelaic acid ormonomethyl azelate. For example, the diacid is at least 40%, 50%, 60%,70%, 80%, 90%, 95%, or 95% pure.

The oxygen that is not consumed in the oxidative ozonolysis may berecycled and/or reused. For example, the unused oxygen may be used forgeneration of water, ozone, or electricity, or a combination thereof, asdescribed herein.

The current invention also provides an ozonolysis process comprising: 1)reacting a fatty acid with ozone to produce an ozonated product; 2)reducing the ozonated product under reductive ozonolysis to produce areduced product; 3) separating an aldehyde from the reduced product; 4)oxidizing the reduced product to produce an oxidized product; and 5)separating a diacid from the oxidized product. In one embodiment, theprocess of the invention further comprises generating ozone prior tostep 1). In one embodiment, step 2) comprises hydrogen gas. In a furtherembodiment, any unused hydrogen gas is recycled. In another embodiment,step 4) comprises oxygen. In a further embodiment, any unused oxygen isrecycled.

An example of the hybrid ozonolysis of the current invention, withoutbeing limited to the example herein, is shown in FIG. 1. As shown in thescheme in FIG. 1, ω-9 oleic acid may be passed through a reactor (A)where gaseous ozone and oxygen may be introduced for reaction with ω-9oleic acid. The oleic acid may react with ozone at the sites ofunsaturation on the fatty acid, and may form a mixture of ozonides,peroxides, and aldehydes, as well as small amounts of acids and/oresters as byproducts. The ozonized oleic mixture may then be passed intoa hydrogenation chamber (B) where peroxides and ozonides may be reducedin the presence of hydrogen and a suitable catalyst. Examples of suchcatalysts include, without being limited to those disclosed herein, Pdor Pt. The hydrogenation process may produce a solution of largelyaldehyde products, with small amounts of carboxylic acid and/or esterbyproducts. In an embodiment, more than about 70% aldehydes areproduced, and less than about 30% of carboxylic acid and/or ester areproduced. In another embodiment, more than about 80% aldehydes and lessthan about 20% of acids and/or ester are produced. In anotherembodiment, more than about 90% aldehydes and less than about 10% ofacids and/or ester are produced.

In an embodiment of the current invention fatty acid (or ω-9 oleic acid,as shown in FIG. 1) may be passed through an ozone reactor as athoroughly mixed emulsion in water. In an embodiment, the entireemulsion may pass through the ozonolysis reactor and the hydrogenationreactor.

The organic phase may then be fractionated, preferably by distillation,but optionally by ion exchange or any other mean, to give a fractioncontaining the desired linear alkyl aldehyde, e.g., nonanal in FIG. 1.The balance of the organic mixture may then be further distilled togenerate a high purity fraction of acid (e.g., 9-oxononanoic acid),which may then be oxidized in an oxidation chamber (C), as shown inFIG. 1. The high purity fraction may also be oxidized in an oxidationchamber (C), with diacid being recovered in high purity after oxidationby distillation, precipitation, and/or extraction.

In one embodiment the purity of 9-oxononanoic acid may be more thanabout 45%. In one embodiment the purity of 9-oxononanoic acid may bemore than about 60%.

The ozone for embodiments of the current invention may be generated fromoxygen using any commercial or non-commercial technology, including acorona discharge apparatus, a water electrolyzer, or from a combinationof a water electrolyzer and a corona discharge apparatus. The oxygenused for the ozone generation may be from any reasonable source,including air, distilled air, and/or, from the electrolysis of water.The hydrogen for this process may be generated by any conventionalcommercial means, including the reformation of natural gas, or,preferably, from the electrolysis of water. Gases may be introduced tothe process but may not fully be consumed and may then be recovered andused for an alternative purpose, recycled into the process, ordiscarded. The oxygen that may be present in the ozone reactor may becarried on for use in the oxidation reactor, or different sources ofoxygen may be used.

In one embodiment of the current invention, any unused or excesshydrogen from the hydrogenation chamber during hybrid ozonolysis may beused to generate water and/or electricity.

In another embodiment, any excess oxygen in the oxidation chamber mayalso be used to generate water and/or electricity, where no oxygen maybe recycled into the ozone reactor and substantially all of the oxygenmay be utilized. Alternatively, unused oxygen from the oxidation chambermay be recycled to the ozone reactor after passing through distillationtowers.

In some embodiments of the current invention, a fuel cell or a gasturbine may be used to generate electricity, which may then be used forelectrolytic production of oxygen and hydrogen for use in the ozonolysisprocess.

The ozonolysis process may be carried out in a continuous fashion, wherefatty acid may be fed into the beginning of the process at a continuousrate over multiple hours and similarly being passed from the initialreactor into subsequent downstream processes at a correspondingcontinuous rate over multiple hours. In one embodiment, the fatty acidand gas in-put flow, and gas and ozonolysis product out-put flow to andfrom chambers may be continuous without interruption. In anotherembodiment, the flow may be with interruption, where the interruptionmay be a single interruption or multiple interruptions. The single ormultiple interruptions, according to some embodiments may be scheduledor random.

General Methods of Ozonolysis

The ozonolysis in the current invention may be carried out undervirtually atmospheric pressure conditions. In this context, virtuallyatmospheric pressure conditions are understood as meaning pressures of 1to about 3 bar, or as is customary in industry in order to preventinfiltration of air into hydrogenation reactor. The reduction of theozonolysis products may be carried out under the virtual atmosphericcondition. In another embodiment, hydrogenation may be carried out underpressure of up to 50 bar, thereby increasing the rate of hydrogenation.

In one embodiment, the ozonolysis process of the current invention maynot require any pressure and may not involve an increase in the rate ofhydrogenation.

The formation of the ozonides and oxidation to form two carboxylic acidgroups may be applicable to compounds containing carbon-carbon doublebonds. In one embodiment, the process can be useful for forming carboxylgroups in compounds containing from about 8 to about 30 carbon atoms andone or more double bonds. Fatty acids such as carboxylic acids, theirnitriles, amides, esters and the like or alkene compounds can or may beused as feed for the process.

The ozonolysis process of the current invention may be incorporated intoother ozonolysis-based chemical manufacturing technologies. Technologieswhere the ozonolysis of the current invention may be included, withoutbeing limited to the examples, include the ozonolysis of oleochemicalssuch as a fatty acid or stereoisomer or ester thereof, a wax ester, or along-chain alkenone. For example, the aliphatic compound is selectedfrom oleic acid, linoleic acid, linolenic acid, gadoleic acid, erucicacid, palmitoleic acid, myristoleic acid, petroselenic acid, vaccenicacid, ricinoleic acid, sappienic acid, stereoisomers thereof, and estersthereof.

The methods of the current invention may be used to or incorporated intoa system to produce a large variety of products based on fats or oilsfor various uses, such as specialties for polymer applications,biodegradable mineral oil replacements for lubricants, and surfactantsand emulsifiers for home and personal-care industries. For example,ozonolysis of oleic acid may produce azelaic acid, which then may beused in producing polyamides (e.g., nylon 6.9, nylon 6.6.9) orpolyurethanes (e.g., laminating adhesives).

An ozone reactor, according to the current invention, may be anycommercially available reactor suitable for incorporation in the methodof the current invention. For example, an OCUBE® (Thales Nano, Inc.)ozonolysis system may be incorporated and/or modified as needed for usein the current invention. The OCUBE® works by continuous-flow of fattyacid, which may be combined with ozone, generated from an in-built ozonereactor, at temperatures between room temperature and −25° C. Theozonide formed may then be immediately mixed with an oxidative orreductive quench reagent, under cooling, to generate the requiredproduct. The product elutes from the reactor in minutes (e.g., for quickanalysis). The ozone production may be turned off, so that other lowtemperature reactions may be performed. The ozonolysis of the currentinvention may be scaled for large scale industrial production with batchsize from about 20 to about 500 kg.

A fuel cell, according to the current invention, may be a device thatconverts the chemical energy from a fuel into electricity through achemical reaction with oxygen or another oxidizing agent. Hydrogen maybe a fuel, but hydrocarbons such as natural gas and alcohols likemethanol may be used. Fuel cells of the current invention are differentfrom batteries in that they may require a constant source of fuel andoxygen to run, but may produce electricity continually for as long asthese inputs are supplied.

Many types of fuel cells are contemplated for use in this invention.Fuel cells will consist of an anode (negative side), a cathode (positiveside) and an electrolyte that allows charges to move between the twosides of the fuel cell. Electrons are drawn from the anode to thecathode through an external circuit, producing direct currentelectricity. As the main difference among fuel cell types is theelectrolyte, fuel cells may be classified by the type of electrolytethey use. Fuel cells may come in a variety of sizes. Individual fuelcells may produce very small amounts of electricity; about 0.7 volts, socells are “stacked,” or placed in series or parallel circuits, toincrease the voltage and current output to meet an application's powergeneration requirements. In addition to electricity, fuel cells mayproduce water, heat and, depending on the fuel source, very smallamounts of nitrogen dioxide and other emissions. The energy efficiencyof a fuel cell may be between 40-60%, up to 85%, or higher if waste heatis captured for use, and if the hydrogen and oxygen are recycled, as inthe current invention.

The current invention may involve a gas turbine for generation ofelectricity. A gas turbine, also known as a combustion turbine, is atype of internal combustion engine. The turbine may have an upstreamrotating compressor coupled to a downstream turbine, and a combustionchamber in-between. Energy may be added to the gas stream in thecombustor, where fuel may be mixed with air and ignited. In the highpressure environment of the combustor, combustion of the fuel mayincrease the temperature. The products of the combustion may be forcedinto the turbine section. In the turbine section, the high velocity andvolume of the gas flow may be directed through a nozzle over theturbine's blades, spinning the turbine which powers the compressor and,for some turbines, drives their mechanical output. The energy given upto the turbine comes from the reduction in the temperature and pressureof the exhaust gas. Various types of gas turbines may be used in thecurrent invention, including aeroderivative gas turbines, auxiliarypower units (APU), industrial gas turbines for power generation,compressed air energy storage, microturbines, miniature gas turbines,and other similar turbines suitable for use in an ozonolysis process, asin the current invention.

General Definitions

In this specification and in the claims that follow, reference is madeto a number of terms, which shall be defined to have the followingmeanings: All temperatures are in degrees Celsius (° C.) unlessotherwise specified.

The following examples are illustrative, but not limiting, of themethods, articles, and materials of the present invention. Othersuitable modifications and adaptations of the variety of conditions andparameters normally encountered in the disclosed method and that areobvious to those skilled in the art are within the spirit and scope ofthe embodiments.

As used herein, the singular forms “a,” “an,” and “the” include pluralreferents unless the context clearly dictates otherwise. Thus, forexample, reference to “a fatty acid” includes not only a single fattyacid but also a combination or mixture of two or more different fattyacids, reference to “a derivative” includes a single derivative as wellas two or more derivatives, and the like.

As used herein, the phrases “for example,” “for instance,” “such as,” or“including” are meant to introduce examples that further clarify moregeneral subject matter. These examples are provided only as an aid forunderstanding the disclosure, and are not meant to be limiting in anyfashion. Furthermore as used herein, the terms “may,” “optional,”“optionally,” or “may optionally” mean that the subsequently describedcircumstance may or may not occur, so that the description includesinstances where the circumstance occurs and instances where it does not.For example, the phrase “optionally present” means that an object may ormay not be present, and, thus, the description includes instanceswherein the object is present and instances wherein the object is notpresent.

As used herein, the terms “ozonated product stream” and “ozonatedproducts” are used interchangeably, and may refer to either singular orplural depending on the context.

EXAMPLES Example 1

Hybrid Ozonolysis

Hybrid ozonolysis of oleic acid, for example, is performed to generateazelaic acid and nonanal. A representative product flow of hybridozonolysis of oleic acid is shown in FIG. 1. ω-9 oleic acid, as shown inFIG. 1, is passed through an ozone reactor as a thoroughly mixedemulsion in water. If the mixture leaving the hydrogenation chamber isbiphasic in the presence of water, a coalescer and/or phase separator isused to separate the desired organic phase from the aqueous layer. Theorganic phase is then fractionated by distillation or by ion exchange,to give a fraction containing the desired linear alkyl aldehyde,nonanal. The balance of the organic mixture is then further distilled togenerate a high purity fraction of 9-oxononanoic acid, which is thenoxidized in an oxidation chamber (C), or is taken on wholly to beoxidized in an oxidation chamber (C), with diacid being recovered inhigh purity after oxidation by distillation, precipitation, and/orextraction. Excess oxygen and/or hydrogen may be recovered for alternateuse, recycled, or discarded. See FIG. 1.

Example 2

Hybrid Ozonolysis—Recycling Hydrogen and Oxygen

A hybrid ozonolysis may be performed following the schematic in FIG. 2.In the schematic in FIG. 2 of gas flow through a hybrid of the reductiveand oxidative ozonolysis processes, the unbroken lines marked with I-IVand the unbroken lines with arrows directing away from chambers C and Drepresent the flow of organic reactants and products. In this method,fatty acid is added to an ozone reactor (B), where ozonolysis of oleicacid or any vegetable oil fatty acid (as an example only) can beinitiated. The ozonated product stream is then partially hydrogenated toproduce aldehydes in a hydrogenation reactor (A). The aldehydes are thendistilled off in a distiller or a distillation tower (C). The remainingozonated product stream is then oxidized in an oxidation chamber (D) togenerate acids. Excess oxygen (from D) and excess hydrogen (from A) arethen fed into a fuel cell to generate electricity and/or water.Optionally, excess oxygen is recycled to the ozone reactor. A schematicof hybrid ozonolysis is shown in FIG. 2.

Example 3

Hybrid Ozonolysis of Fatty Acid Derived from Algae

Fatty acid derived from algae was used as a starting material. Thecomposition of this fatty acid was determined using the methyl esterderivatization technique described in AOAC Official Method 969.33 FattyAcids in Oils and Fats. Official Methods of Analysis of the AOAC, 17thedn, AOAC, Arlington, Va. USA, (2000), followed by GC FID analysis, theresults of which are shown in FIG. 3. According to peak integration, thestarting fatty acid was determined to be about 84% oleic acid.

Ozonolysis

300 g of fatty acid derived from algae was combined with 300 g of waterin a 2 liter batch reactor and stirred at 800 rpm with an initialtemperature of 20° C. Ozone was then sparged through the mixture at arate of 6.5 liters per minute and a concentration of 75 g/m³ ozone for100 minutes. The temperature rose during the reaction but did not exceed50° C. After 100 minutes, the reaction mixture was purged of O₂ and O₃by sparging with N₂.

Reduction

The aqueous mixture of ozonated fatty acid derived from algae was thentransferred to a high-pressure vessel and charged with 0.25% by wt.palladium black and placed under 350 psi H₂ at 70° C. The reactionmixture was vigorously stirred for 80 minutes and then the reaction wasbrought to ambient pressure and filtered to remove catalyst while thereaction mixture was still >40° C., or ˜60° C. The organic and aqueousphases readily separated and the organic phase was partitioned off for˜280 g of organic material. Slightly less than theoretical was obtainedlargely due to transfer losses between vessels. A GC FID trace of thismaterial can be seen in FIG. 4. Note that not all molecules aresufficiently volatile to be seen in this trace, specifically stearicacid, however, when used in conjunction with calibration curves it isestimated that the organic phase is ˜25% nonanal and ˜7.7% nonanoicacid.

Separation

A short path wiped film evaporator (Incon ICL-04) was then used tofractionate the organic material. The organic material (280 g) was addeddropwise to the distillation chamber, which was kept at a reducedpressure of 0.8-1.0 mbar. The distillation surface was kept at 50° C.while the condenser temperature was kept at 0° C. and the cold trap waskept chilled with dry ice. Distillate (69 g) was recovered that wasdetermined to be >97% nonanal by GC FID (FIG. 5). Heavy residue (190 g)was also collected that turned to a white solid upon cooling to roomtemperature. The balance of volatile material was collected in the dryice trap.

Oxidation

A portion of the white, heavy residue from separation was analyzed usinga modification of the methyl ester derivatization technique described inAOAC Official Method 969.33 Fatty Acids in Oils and Fats. OfficialMethods of Analysis of the AOAC, 17th edn, AOAC, Arlington, Va. USA,(2000). The sole modification was the omission of alkaline, which wouldhave degraded the aldehydic materials present in the sample. Using thismodified method, the majority, but not all, of the aldehydes wereconverted to the corresponding dimethyl acetal. GC FID analysis of thesemethyl ester/acetal derivatives suggested that the material was ˜42%azelaldehyde (i.e., 9-oxononanoic acid) and ˜8% azelaic acid with muchof the balance being nonanoic acid (˜6.8%), palmitic acid (14%) andstearic acid (24.55%). This result can be seen in FIG. 6. Note thatazelaldehyde is represented by peaks at 9.996 min (assigned asazelaldehyde methyl ester) and 10.214 min (assigned as azelaldehydemethyl ester dimethyl acetal).

61.2 g of the white, heavy residue from separation step was charged with104.8 mg of Mn(OAc)₂ in a round bottom flask and was heated to 75° C. O₂was then sparged through the mixture using a coarse frit for 3 hours.100 ml of H₂O was added to the mixture to remove all solids from thesidewall of the flask and sparging was continued for another 2 hours.The organic phase was then extracted with H₂O at elevated temperature(>50° C. or ˜70° C.) two times with 150 ml H₂O and two times with 100 mlH₂O. The aqueous fractions were then extracted with heptane two times(100 ml heptane each) at elevated temperature. The aqueous phase wasthen allowed to cool to room temperature. Upon cooling white crystalsformed in the aqueous layer, which were then collected with filtration.After drying under high vacuum, 18.5 g of white crystals were obtained.An analytical sample was then derivatized as the methyl ester using theaforementioned modification of AOAC Method 969.33 Fatty Acids in Oilsand Fats. Official Methods of Analysis of the AOAC, 17th edn, AOAC,Arlington, Va. USA, (2000), and analyzed using GC FID, the results ofwhich can be seen in FIG. 7. Integration suggested the material is >97%azelaic acid. Some azelaic acid still remained in the organic phase andcould be recovered with additional hot aqueous extractions. The heptaneextraction should be regarded as an optional step that results in aslightly improved purity of the recovered azelaic acid.

Example 4

Hybrid Ozonolysis of Methyl Canolate with Methyl 9-OxononanoateIsolation

Methyl canolate (also known as canola oil fatty acid methyl ester) wasprepared according known procedures for converting vegetable oils intofatty acid methyl esters. According to GC analysis the composition ofthis material is as follows: methyl oleate (57.36%), methyl palmitate(4.17%), methyl linoleate (20.27%), methyl linolenate (8.2%), and methylstearate (1.83%).

Ozonolysis

Methyl Canolate (300 g) was combined with 600 g of H₂O and was cooled to20° C. while vigorously stirring. Ozone was introduced to the system ata flow rate of 7 L/min with a maximum concentration of 100 g/m³ for atotal of 110 minutes. GC FID indicated greater than 95% consumption ofstarting material. The reaction mixture was then purged with N₂ and wastaken on as it was without further purification.

Reduction

The aqueous mixture of oxidized methyl canolate was combined with 0.25%Pd black (by wt. of methyl canolate), placed under 350 psi of H₂pressure, and was heated to 75° C. until peroxide titration indicatedthe absence of peroxide. The mixture was then removed from heat andpressure and was filtered to recover Pd. The resulting mixture wasbiphasic and quickly phase separated in an extraction funnel. The top,organic phase (a light yellow liquid; 293 g) was partitioned off andcarried on as it was. (Note: after extraction of the aqueous phase withethyl acetate, another 5 g of organic material was recovered and was setaside).

Separation

A short path wiped film evaporation system (Pope Scientific 2″ WipedFilm Still) was then used to fractionate the organic material. 293 g ofliquid was loaded into the feeder and was fed dropwise down the columnwhich was maintained at 1.0-1.1 mbar pressure with a 50° C. jackettemperature, a −10° C. condenser temperature, and a dry ice/acetonetrap. 100.3 g of light aldehydic material was evaporated off consistingof mostly nonanal and hexanal. The resulting heavy residue (179 g) wasagain distilled on the wiped film evaporator under 0.2-0.3 mbar pressurewith a 50° C. jacket temperature, a −10° C. condenser temperature, and adry ice/acetone trap. 46 g of methyl 9-oxononanoate was isolated in thedistillate at greater than 80% purity. This material can be taken on foroxidation as described in example 3 or can be taken on for other uses.

Example 5

Oxidation and Crystallization of an Acid—Ester, Monomethyl Brassylate

Following procedures similar to those described in previous examples,500 g of methyl erucate (89% by GC FID) was ozonolyzed, reduced, anddistilled to remove the majority of the light alkyl aldehydes (almostexclusively nonanal), resulting in 380 g of heavy residue containinglargely nonanoic acid, 13-oxotridecanoate methyl ester, and monomethylbrassylate. This material was taken as was for oxidation andcrystallization as described below.

Oxidation

The heavy residue (380 g) was charged with 380 mg of Mn(OAc)₂ and washeated to 100° C. while sparging with O₂ and stirring. The solutionturned a dark brown and was left to react for 160 minutes until GCindicated that all 13-oxotridecanoate methyl ester was converted to thecorresponding acid, monomethyl brassylate. This material was then takenup in heptane (3× the weight of the substrate) and was heated to 90° C.Upon cooling crystals formed which were then filtered. These crystalswere then again recrystallized from hot heptane, resulting in 60 g ofmonomethyl brassylate as a white crystalline solid. GC FID of thismaterial is shown in FIG. 10, and the ¹H NMR in FIG. 11. The balance ofthe material can be continuously crystallized in this fashion to isolateadditional monomethyl brassylate.

EQUIVALENTS

The invention can be embodied in other specific forms without departingfrom the spirit or essential characteristics thereof. The foregoingembodiments are therefore to be considered in all respects illustrativerather than limiting on the invention described herein. Scope of theinvention is thus indicated by the appended claims rather than by theforegoing description, and all changes that come within the meaning andrange of equivalency of the claims are intended to be embraced therein.

What is claimed is:
 1. A method comprising: a) providing oxygen andhydrogen, wherein said oxygen treated with electricity to generateozone; wherein said ozone is used in ozonolysis of a fatty acid or afatty acid ester in an ozone reactor; b) inputting said fatty acid intosaid ozone reactor, in which said fatty acid or fatty acid ester absorbssaid ozone, thereby forming a mixture comprising ozonated product streamcomprising one or more compounds selected from ozonide, peroxide,aldehyde, ester, and acid; and c) generating partially reduced productscomprising a linear alkyl aldehyde and oxygenated products comprising adiacid or acid-ester from said ozonated product stream by: i. partiallyreducing said ozonated product stream after said ozonated product streamenters a hydrogenation chamber to generate said partially reducedproducts comprising largely a linear alkyl aldehyde, and contacting saidpartially reduced products with water, forming two layers comprising anorganic phase while leaving the hydrogenation chamber; j. fractionatingsaid organic phase to separate said linear alkyl aldehyde from theremaining organic phase; and k. oxidizing the remaining organic phaseafter fractionation at step (j) after the remaining organic phase entersinto an oxidation chamber, resulting in the generation of saidoxygenated products comprising said diacid or acid-ester; therebygenerating said linear alkyl aldehyde and said diacid or acid-ester fromsaid ozonated product stream, wherein the linear aldehyde, oxo-acid,oxo-ester, acid-ester, or diacid is more than about 95% pure.
 2. Themethod of claim 1, wherein the linear aldehyde, oxo-acid, oxo-ester,acid-ester, or diacid is more than about 99% pure.